Creamy low-foam liquid built detergent composition



United States Patent "ice 3,037,936 CREAMY LOW-FOAM LIQUID BUILT DETERGENT COMPOSITION William A. Tidridge, Fanwood, and Leon E. Cohen,

Roselle, N.J., assignors to FMC Corporation, a corporation of Delaware No Drawing. Filed June 2, 1958, Ser. No. 738,997 11 Claims. (Cl. 252139) This invention relates to an improved liquid built detergent. More particularly, this invention relates to a stable, creamy built low foam liquid detergent. This invention also relates to a process for the preparation of the liquid detergent.

A good built liquid detergent should contain all of the essential ingredients of a good built dry detergent formulation, Le, a surfactant, a phosphate builder, an anti-corrosion agent and an anti-redeposition agent. In addition, a foam stabilizer is sometimes necessary when a high persistent foam is desirable, and other ingredients such as optical brighteners, dyes, perfumes, etc. may be incorporated where desired. However, it has not been commercially possible heretofore, to incorporate these various ingredients into a liquid formulation and still in separation of the detergent into two or more incornpatible layers. This has been a serious detriment to commercialization of built liquid detergents in the past. Recombination of the separated detergent before use is often difiicult, in addition to being a nuisance. Unless the recombination is performed with care, it results in the use in each washing operation of an improperly blended detergent with resulting decrease in the performance of the detergent.

In efforts to overcome the above mentioned disadvantages, detergent formulators have heretofore resorted to a number of undesirable devices. Sodium silicate is ditiicult to incorporate into liquid detergent formulations and one common device is to leave out this essential ingredient or to decrease its concentration to much less than that necessary for proper protection of metal surfaces which come in contact with the liquid detergent. This results in excessive corrosion of metal containers and of metal Washing machine parts. Another device is to omit sodium carboxymethyl cellulose from the formulation resulting in increased greyness of fabrics laundered with such detergents. Another device is to reduce the proportions of the essential ingredients in the liquid formulation, but this results in poorer performance unless proportionately large amounts of the detergent are used in the washing operation. This results in higher cost to the consumer. Moreover, simple dilution of the liquid detergent does not by itself necessarily permit incorporation of the proper amount of certain ingredients such as sodium silicate and sodium carboxymethyl cellulose.

It is an object of this invention to provide a stable, low foam, built liquid detergent. It is a further object of this invent-ion to provide a stable liquid detergent which contains all of the essential ingredients of a good dry detergent formulation. It is another object of this invention 'to provide a stable liquid detergent employing cheap commercially available materials. Furthermore it is an object of this invention to provide a process for the preparation of these stable low foam built liquid detergents.

According to this invention there is provided a creamy low foam stable built liquid detergent comprising tetrapotassium pyrophosphate, a sodium silicate, carboxymethyl cellulose, propylene glycol, and a surfactant comphosphate is first dissolved in water.

3,037,936 Patented June 5, 1962 prising a compound selected from the group consisting of alkyl aryl polyoxyethylene alcohols, polyoxyethylene esters, and aliphatic polyoxyethylene ethers. It will be' noted that the above identified surfactants are non-ionic surface active agents. If desired a foam stabilizer such as fatty acid alkanol amides, water soluble dyes and antitarnishing agents for metal surfaces may be included in the above formulation.

In the above compositions the pyrophosphate is employed as the phosphate builder and the sodium silicate functions as an anti-corrosion agent. The non-ionic surface active agents are employed as surfactants, and the sodium carboxymethyl cellulose as an anti-redeposition agent.

Hereinafter when referring to the weight of silicate employed it will be understood that it has been calculated as percent S102.

The formulations of this invention may contain from about 12.5 to about 22.0% by weight tetrapotassiurn pyrophosphate, from about 0.1 to about 1.7% by weight silica in the form of a sodium silicate in which the ratio of Na O to Si0 may vary from about 1:1 to about 1:32, from about 1.7 to about 2% by weight propylene glycol, from about 2.5 to about 13.5% by weight of a surfactant selected from the group consisting of alkyl aryl polyoxyethylene alcohols, polyoxyethylene esters and aliphatic polyoxyethylene ethers, up to about 3.5% by weight carboxymethyl cellulose and from about 58 to about by weight Water.

The amount of phosphate that may be employed in the formulation varies inversely with the surfactant used. The critical range of pyrophosphate as indicated above is from about 12.5 to about 22 Weight percent. The critical range of the surfactant concentration varies with the phosphate concentration from a maximum of about 2.5 to about 13.5 weight percent at 12.5 weight percent tetrapotassium pyrophosphate to a minimum of about 5.0 weight percent to about 13 weight percent at 22% tetrapotassium pyrophosphate. The car-boxymethyl cellulose varies with the surfactant employed. For example, when an alkyl aryl polyoxyethylene alcohol is employed the carboxymethylcellulose will vary from about 3 to about 3.5%. When a polyoxyethylene ester or an aliphatic polyoxyethylene ether is employed no more than about 1.5% carboxymethyl cellulose should be used. Care must be taken that the recommended level of the carboxymethyl cellulose content is not exceeded otherwise an undesirable gummy gel may be formed.

The alkyl aryl polyoxyethylene alcohol employed as a surfactant is preferably the product marketed by Rohrn & Haas under the trademark Triton X100, the polyoxyethylene ester is preferably the surfactant marketed by Monsanto under the trademark Sterox CD and the aliphatic polyoxyethylene ether is preferably the surfactant marketed by Monsanto under the trademark Sterox Al. Triton X- is the condensation product of octyl phenol with from 9 to 10 moles of ethylene oxide; Sterox CD is the condensation product of tall oil with about 12 moles of ethylene oxide; Sterox AJ is the condensation product of tridecy-l alcohol with about 8 moles of ethylene oxide. The carboxymethyl cellulose is preferably the product put out by Hercules Powder under the trade name Hercules CMC-70M.

In order to obtain the desired products, the procedure which will be described below must be followed. Deviation from this procedure results in undesirable products.

According to this procedure the tetrapotassiurn pyro- The carboxymethyl cellulose is then brought into solution utilizing the heat of solution of the tetrapotassium pyrophosphate to aid in dispersing. The non-ionic surfactant is then added and blended into the mixture.

it is thoroughly blended into the formulation before proceeding. The propylene glycol is then blended into tation. The product obtained was a gummy gelatinous mixture which could not be poured or handled properly.

Examples 310 Examples Component I etrap tassium Pyrophosphate l2. 5 12.5 12. 5 12. 5 22.0 22.0 22.0 22.0 Silicate 1:3 .22 (NazO/SiOg) in 5. 25 5. 25 5. 25 5. 25 5. 25 5. 25 5. 25 5. 25

GMC 3. O 3.0 3.0 3.0 3. 0 3.0 3.0 3.0

Propylene G1ycol V l. 7 1. 7 1. 7 1. 7 1. 7 1. 7 1. 7 1. 7

ater 62. 55 64. 05 75. 05 76. 05 54. 05 55. 05 63. 05 65. 55

the mixture. The most critical step in the procedure is the incorporation of the silicate at this point. In order to prevent gelation the silicate must be added slowly and with vigorous agitation. It has beenfound that mixing is best accomplished with a high speed mixer, similar in Examples 11-19 Examples Component Tetrapotassium Pyrophosphate 20 0 20.0 20.0 20.0 20.0 20.0 20.0 20 0 20.0 Silicate 1:1 (NazO/SiOz) 3. 3 1 2 Silicate 1:3.22 (NazO/SiO 5. 75 2. 16 5. 5. 25 5. 25 5. 25 5. 25 0M0 5. 0 3. 0 3.0 3.0 3. 0 1. 5 1. 5 3.0 3.0 Alkylaryl Polyoxyethylene Alcohols 10.0 10.0 10.0 10.0 10.0 10. 0 10. 0 Polyoxyet-hylene Ester 10. O Aliphatic Polyoxyethylene Ethers- 10. 0 Propylene Glycol 1. 1. 7 l. 1. 7 1. 7 1. 7 1. 7 2. 0 2. 5 Water- 59. 55 62. 00 64. 10 64. 04 59. 95 61. 45 61. 45 59. 75 59. 25 Brightener, Dye- 0. 1 0.1 0.1 0.

action to the Eppenbach Homo-Mixer. This type of mixer allows for mixing without the entrainment of air.

It has been found that the presence of entrained air causes the dispersion to become unstable. Formulations prepared according to the above procedure have been found A detergent having the following composition was prepared by the following procedure:

Percent Tetrapotassiurn pyrophosphate 20 Liquid silicate (Na O/SiO 1:3.22) 5.3 Carboxymethyl cellulose 3 Propylene glycol 1.7 Alkyl aryl polyoxyethylene alcohol 10 Water 60 The tetrapotassium pyrophosphate was first dissolved in about 60 parts of water. The carboxyrnethyl cellulose was then brought into solution utilizing the heat of solution of the tetrapotassium pyrophosphate. The alkyl aryl polyoxyethylene alcohol was then added and thoroughly mixed into the formulation before any additional ingredients were added. The propylene glycol was then The liquid silicate was then added slowly to the mixture with Vigorous agitation. The resultant detergent Wasa creamy stable liquid which remained stable for many months.

Example 2 The detergent of Example 1 was prepared by the following procedure. The propylene glycol was first dissolved in water. The surface-active agent was then in- 1 oorporated in the mixture. The tetrapotassium pyrophosphate was added, followed by the carboxymethyl cellulose. Finally the silicate was added with vigorous agi- The formulations listed in Examples 11 to 19 were prepared by the procedure described in Example 1. These examples demonstrate the compatibility of the formulation with the different type non-ionic surfactants and the compatibility of the formulations with such minor components as optical hrighteners and dyes. The formulation of Example 19 was unstable due to the use of more than the critical amount of propylene glycol.

The detergents of this invention are all-purpose detergents and are useful for laundering cotton, woolen goods and fine fabrics, for cleaning hard surfaces, and for other wetting and detergent applications such as wetting and emulsifying agents for insecticides.

' 7 Example 20 The detergent properties of the creamy built liquid detergent of Example 1 are tested by techniques similar to those described in the manual Detergency Evaluation and Testing by J. C. Harris, and published by Interscience Publishers Inc. (1954). A simple wash technique is carried out in a Launder-Ometer at 140 F., using two commercially soiled cotton fabrics (Foster D. Snell Soiled Cotton 159 and American Conditioning House in distilled water and with three commercially soiled cotton fabrics (Foster D. Snell Soiled Cotton 159, American Conditioning House 115 and American Conditioning House in 21 g.p.g. synthetic hard water. A redeposition test is carried out in the Launder-Ometer, using bleached, desized Indian Head cotton fabric and a 0.0025 suspension of carbon black in 0, 6, 12, and 18 g.p.g. synthetic hard water at F. Concentration of the built liquid detergent in the test is 0.50%, equivalent to 0.20% solids. Duplicate tests are run simultaneously with a 0.20% solution of a commercially available solid spray-dried detergent having the following approximate composition:

Percent Sodium tripolypho-sphate 50.00 Sodium silicate (as SiO 3.25 Anionic surfactant mixture 22.85 Sodium carboxyrnethyl cellulose 0.20

Percent Sodium sulfate 17.00 Water, perfume and other minor ingredients 6.70

In the following table, the numbers represent the increase in reflectance of the soiled fabrics during the single wash. Each number represents the average of six refl ctance readings made on three replicate fabric samples.

In the carbon redeposition test in 0, 6, 12 and 18 g.p.g. synthetic hard water, three replicate swatches were used at each hardness and the numbers represent the average of six reflectance readings. The values indicate decrease in reflectance (or increased greying) of the original clean white swatches.

Detergent Spray- Water Hardness, g.p.g. o Dried Example 1 Detergent We claim: 1. A stable creamy liquid low-foam built detergent composition which consists essentially of:

(a) from about 12.5 to 22% by weight tetrapotassium pyrophosphate,

(b) from about 0.1 to about 1.7% by weight sodium silicate calculated as silica in which the ratio of Na O/SiO may vary from about 1:1 to 1:3.2,

(0) from about 1.7 to 20% by weight propylene glycol,

(d) from about 58 to 80% by Weight water,

(e) from about 2.5 to 13.5% by weight of a surfaceactive agent selected from the group consisting of the condensation product of octyl phenol with from 9 to 10 moles of ethylene oxide, the condensation product of tall oil with about 12 moles of ethylene oxide, and the condensation product of tridecyl alcohol with about 8 moles of ethylene oxide,

(1) and sodium carboxymethyl cellulose in amounts up to 3.5% by weight.

2. A stable creamy liquid low-foam built detergent composition Which consists essentially of:

(a) about 12.5% by weight tetrapotassium pyrophosphate,

(b) from about 0.1 to about 1.7% by weight sodium silicate calculated as silica in which the ratio of Na O/SiO may vary from about 1:1 to 1:32,

(c) from about 1.7 to 2.0% by weight propylene glycol,

(01) from about 58 to 80% by weight water,

(e) from about 2.5 to 13.5% of a surface-active agent selected from the group consisting of the condensation product of octyl phenol with from 9 to 10 moles of ethylene oxide, the condensation product of tall oil with about 12 moles of ethylene oxide, and the condensation product of tridecyl alcohol with about 8 moles of ethylene oxide,

(f) and sodium carboxymethyl cellulose in amounts up to 3.5% by weight.

3. A stable creamy liquid low-foam built detergent composition which consists essentially of:

(a) about 22% by weight tetrapotassium pyrophosphate,

(b) from about 0.1 to about 1.7% by weight sodium 6 silicate calculated as silica in which the ratio of Na O/SiO may vary from about 1:1 to 123.2,

(c) from about 1.7 to 2.0% by weight propylene glycol,

(d) from about 5.0 to 13% by weight of a surfaceactive agent selected from the group consisting of the condensation product of octyl phenol with from 9 to moles of ethylene oxide, the condensation product of tall oil with about 12 moles of ethylene oxide, and the condensation product of tridecyl alcohol with 10 about 8 moles of ethylene oxide,

'(e) and sodium carboxymethyl cellulose in amounts up to 3.5 by weight,

(1) the balance being water.

4. A stable creamy liquid low-foam built detergent com- 15 position which consists essentially of:

(a) from about 12.5 to 22% by weight tetrapotassium pyrophosphate,

(b) from about 0.1 to about 1.7% by weight sodium silicate calculated as silica in which the ratio of Na O/SiO may vary from about 1:1 to 1:3.2,

(0) from about 1.7 to 2.0% by weight propylene glycol,

(d) from about 58 to 80% by weight water.

(:2) from about 2.5 to 13.5% by weight of the condensation product of octyl phenol with from 9 to 10 moles 25 of ethylene oxide,

(f) and from about 3 to 3.5% by weight sodium carboxy-methyl cellulose.

5. The detergent composition of claim 4 wherein said tetrapotassi-um pyrophosphate is present in the amount of about 12.5% by weight.

6. The detergent composition of claim 4 wherein said tetrapotassium pyrophosphate is present in the amount of about 22% by weight.

7. A stable creamy liquid low-foam built detergent composition which consists essentially of:

(a) from about 12.5 to 22% by weight tetrapotassium pyrophosphate,

(b) from about 0.1 to about 1.7% by weight sodium silicate calculated as silica in which the ratio of Na O/SiO may vary from about 1:1 to 1:32,

(c) from about 1.7 to 2.0% by weight propylene glycol,

(d) from about 58 to 80% by weight water,

(e) from about 2.5 to 13.5% by weight of a surfaceactive agent selected from the group consisting of the condensation product of tall oil with about 12 moles of ethylene oxide, and the condensation product of tridecyl alcohol with about 8 moles of ethylene oxide,

(f) and sodium carboxymethyl cellulose in amounts up to 1.5% by weight.

8. The detergent composition of claim 7 wherein said tetrapotassium pyrophosphate is present in the amount of 12.5% by weight.

9. The detergent composition of claim 7 wherein said tetrapotassium pyrophosphate is present in the amount of about 22% by weight.

10. A stable creamy liquid low-foam built detergent composition which consists essentially of:

(a) about 20% by weight tetrapotassium pyrophosphate,

(b) from about 0.1 to about 1.7% by weight sodium silicate calculated as silica in which the ratio of Na O/SiO- may vary from about 1:1 to 123.2,

(0) about 1.7% by weight propylene glycol,

(d) about 60% by weight water,

(e) about 10% by weight of the condensation product of octyl phenol with from 9 to 10 moles of ethylene oxide, (7) and about 3% by weight sodium carboxymethyl cellulose.

11. A method for the production of a stable creamy liquid low-foam built detergent composition which consists essentially of: I

(a) dissolving about 12.5 to about 22% by weight tetrapotassium pyrophosphate in from about 58 to by weight water,

(b) adding sodium carboxymethyl cellulose to the pyrophosphate solution, said sodium carboxymethyl cellulose being added in amounts up to 3.5% by weight, 7

(c) adding from about 2.5 to 13.5% by weight of a surface-active agent selected from the group consisting of the condensation product of octyl phenol with from 9 to 10 moles'ethylene oxide, the condensation product of tall oil with about 12 moles of ethylene oxide, and the condensation product of tridecyl alcohol with about 8 moles of ethylene oxide,

(d) thoroughly blending said surface-active agent in the mixture before proceeding,

(e) blending about 1.7 to 2.0% by weight propylene glycol into the mixture,

(f) and finally adding with vigorous agitation from about 0.1 to 1.7% by weight sodium silicate calculated as silica in which the ratio Na O/SiO may vary from about 1:1 to 1:32.

References Cited in the tile of this patent UNITED STATES PATENTS 2,560,839 Ayo et a1. July 17, 1951 2,864,770 McCune et a1 Dec. 16, 1958 FOREIGN PATENTS 738,585 Great Britain Sept. 25, 1957 550,740 Belgium Dec. 30, 1956 OTHER REFERENCES The American Perfumer and Essential Oil Review,

article by Harris, November 1946, pp. 54-56.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 3,037,936 June 5 1962 William A. Tidridge et a1.

It is hereby certified that error appears in the above numbered petent requiring correction and that the said Letters Patent should read as corrected below.

Column 5, line 42, for "20%" read 2.0%

Si ned and sealed this 16th day of October 1962.

SEA L) ,ttest:

RNEST w. SWIDER DAVID LADD ,ttesting Officer Commissioner of Patents 

1. A STABLE CREAMY LIQUID LOW-FOAM BUILT DETERGEN COMPOSITION WHICH CONSISTS ESSENTIALLY OF: (A) FROM ABOUT 12.5 TO 22% BY WEIGHT TETRAPOTASSIUM PYROPHOSPHATE, (B) FROM ABOUT 0.1 TO ABOUT 1.7% BY WEIGHT SODIUM SILICATE CALCULATED AS SILIKCA IN WHICH THE RATIO OF NA2O/SIO2 MAY VARY FROM ABOUT N1:1 TO 1:3.2, (C) FROM ABOUT 1.7 TO 20% BY WEIGHT PROPYLENE GLYCOL, (D) FROM ABOUT 58 TO 80% BY WEIGHT WATER, (E) FROM ABOUT 2.5 TO 13.5% BY WEIGHT OF A SURFACE ACTIVE AGENT SELECTED FROM THE GROUP CONSISTING TO THE CONDENSATION PRODUCT OF ETHYLENE OCTYL PHENOL WITH FROM 9 TO 10 MOLES OF ETHYLENE OXIDE, THE CONDENSATION PRODUCT OF TALL OIL WITH ABOUT 12 MOLES OF EHTYLEN OXIDE, AND THE CONDENSATION PRODUCT OF TRIDECYL AL COHOL WITH ABOUT 8 MOLES OF ETHYLENE OXIDE, (F) AND SODIUM CARBOXYMETHYL CELLULOSE IN AMOUNTS U$ TO 3.5% BY WEIGHT. 